Accepted Manuscript

Most common surfactants employed in chemical enhanced oil recovery

Chegenizadeh Negin, Saeedi Ali, Quan Xie

PII: S2405-6561(16)30062-1
DOI: 10.1016/j.petlm.2016.11.007
Reference: PETLM 117

To appear in: Petroleum

Received Date: 13 May 2016

Revised Date: 7 November 2016
Accepted Date: 28 November 2016

Please cite this article as: C. Negin, S. Ali, Q. Xie, Most common surfactants employed in chemical
enhanced oil recovery, Petroleum (2017), doi: 10.1016/j.petlm.2016.11.007.

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 ACCEPTED MANUSCRIPT

1 Most Common Surfactants Employed in Chemical Enhanced Oil Recovery

2 Chegenizadeh Negin, Saeedi Ali, Quan Xie
3 Abstract
4 Chemical enhanced oil recovery (EOR) and particularly surfactant injection has recently
5 received a great deal of attention. The suggested recovery mechanisms after injecting surfactants

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6 include wettability alteration and IFT reduction. If a surfactant is properly selected according to
7 the environmental variables- such as pressure, temperature, salinity, it can lead to more efficient
8 enhanced recovery from an oil reservoir. On the other hand, poor selection of the surfactant can

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9 result in a low recovery and can even become detrimental to the reservoir due to undesirable
10 wettability alteration and possible rock dissolution resulting in a chemical reaction with
11 displacing fluid and blockage of the pore space. Also, choosing the wrong surfactant without

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12 considering the rock mineralogy may result in high adsorption on the pore surface of the rock
13 and unnecessary waste of resources. It is also worthy to note that surfactants are some of the
14 most expensive chemicals used during EOR. Extensive literature review suggests that anionic

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15 surfactant are the preferred surfactant category for EOR especially when it comes to sandstone
16 reservoirs. Occasionally, in specific situations a better performance have been reported after
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17 injecting cationic, non-ionic or mixtures of both surfactants, particularly when dealing with
18 carbonate reservoirs. This paper presents in detail a review of the most commonly applied
19 surfactants in EOR studies and the optimum application criteria for of each type. To the best of
20 the authors’ knowledge, such detailed and comprehensive review is not available in the
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21 literature, presently.
22
23 Keywords: Surfactants, Enhanced Oil Recovery, Wettability, Interfacial Tension
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24
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25 Introduction
26 Mechanisms of surfactant EOR mainly include decreasing interfacial tension (IFT) and shifting
27 reservoir wettability towards strongly water-wets. The remaining oil saturation can be divided
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28 into two categories, firstly residual oil to water flooding, which usually is attached at pore wall,
29 and secondly oil bypassed by the water flooding. Typically, the residual oil saturation will be in a
30 range of 20 to 30% OOIP within contacting 100% of given oil zone by water flooding. The oil is
31 immobile at this saturation range due to the surface tension between oil and water. Also, the
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32 differential pressure alone cannot overcome the high capillary pressure to move oil out from
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33 pores. However, the surfactants can reduce the interfacial tension, thereby decrease capillary
34 pressure and allow water to remove the trapped oil as a result of water bypass. Furthermore,
35 surfactant can also drive the reservoir wettability towards more water-wet and lifting off the
36 attached oil film from the pore wall, thus decreasing residual oil saturation and enhancing oil
37 recovery.
38
39 The concept of applying surfactants in enhanced oil recovery was introduced in the early 1900’s.
40 The initial unsuccessful efforts led to the creation of a new revolutionary theory related to the
41 possibility of producing in-situ surfactants. This idea was initiated from the fact that naphthenic

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1 acids exist in the reservoir, naturally. The main question to be answered about this technique was
2 whether the soap or, in other words, the surfactant would be produced once an alkali is injected
3 into the pore space of the rock. Although this method had the potential to reduce the cost of
4 injecting synthetic surfactants, the results achieved were not convincing in order for the method
5 to be announced successful. Finally in the 1960s, yet again the research in this area focused on
6 the use of synthetic surfactants, however, this time mainly on designing surfactants tailored for

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7 each specific circumstance using the less expensive raw material. In the 1980’s, combining the
8 benefits of alkali and surfactants resulted in the invention of one of the most important methods
9 of chemical EOR called alkaline-surfactant-polymer, (ASP). Since then, tremendous amount of

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10 research work has been carried on designing different surfactants according to the situations at
11 hand, however unfortunately there is no single body of text available in the literature to provide
12 researchers with an overview of the various research work conducted to date and their outcomes.

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13 This paper is an attempt to bridge this gap in the literature and provide an overview of the history
14 of surfactants and their use in EOR. In addition, since variation in the formation water salinity,
15 oil composition and temperature can affect the performance of the surfactants by impacting on
16 the interfacial tension (IFT) and wettability, the optimum conditions for the application of each

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17 reviewed surfactant are also discussed.
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19 Significance of Operational Conditions
20 Decreasing interfacial tension and shifting reservoir wettability towards more water-wet are the
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21 main mechanisms of surfactant flooding in the reservoirs. To remove the alcohol and increase
22 the solubilisation of oil and water in microemulsions, surfactants with branched hydrocarbon
23 chains, adding ethylene oxide (EO), decreasing the hydrophilic propylene oxide (PO) groups to
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24 the surfactant are used[1]. Based on the survey results, decreasing interfacial tension has long
25 been the goal of chemists to enhance oil recovery by developing economical surfactant for
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26 sandstone reservoirs[2]. However, for carbonated reservoirs, reservoir engineers have been
27 focusing on using cationic surfactants to drive the reservoir wettability from oil-wet to water-
28 wet, thus accelerating the oil production rate by decreasing the residual oil saturation.
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29
30 Temperature
31 Karnanda et al. [3] explained that most of the surfactant solutions have a cloud point temperature
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32 beyond which the solution becomes cloudy and measuring the IFT or other parameters become
33 almost impossible. However, the anionic surfactants solution have a Krafft point temperature,
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34 suggesting that the surfactants would precipitate as the temperature is lower that the Krafft point
35 temperature. At this point, a surfactant becomes ineffective and drops out of the aqueous
36 solution. Depending on the surfactant structure the cloud point temperature can be between 30℃
37 and 160℃. Temperature can affect the IFT and critical micelle concentration (CMC) of
38 surfactant systems and this effect is greater for anionic surfactants. Surfactants’ phase separation
39 (cloud point) at high temperatures could likely lead to the decrease of surfactant’s concentration,
40 thus exhibiting poor performance to decrease IFT [1]. Also, increasing temperature can shorten
41 the time of an interfacial tension to reach equilibrium for Gemini surfactant solutions. However,
42 the temperature plays a minor role for a mixing surfactant system because of synergism [4].

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1 Hiemenz and Rajagopalan [5] in their book define CMC as a concentration level, at and above
2 which the micelles which are the aggregation of surfactant molecules starts to form. CMC is an
3 important factor in studying surfactants. After this threshold, the surfactant behavior, especially
4 its surface tension, stabilizes and stays constant regardless of any increase in its concentration.
5 Most of the experiments in the literature indicate that temperatures above 120℃ results in either
6 degradation or precipitation of most of the surfactant.

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8 Interfacial Tension (IFT)
9 Udeagbara [6] defines IFT as the force that exists between the molecules of the interface

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10 between two fluids. Subsequently, IFT holds these molecules together. A surfactant can reduce
11 this force by getting adsorbed at the interface between two liquids or a liquid and a gas. Troy et
12 al. in their book [7] explain that this force is often measured in dynes/cm and it can be affected

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13 by pressure, temperature, and the composition of each phase. Karnanda et al.[3] explained that
14 lowering this force to low enough values can increase the oil recovery significantly. This is
15 because the IFT gives rise to capillary forces in the porous media which are mainly responsible
16 for the hydrocarbon trapped in the form of residual saturation.

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18 Optimal salinity
19 In general, salinity has a significant effect on a surfactants’ performance. In most of the cases,
20 high salinity has an adverse impact on the efficiency of the surfactant, therefore in a high salinity
21 situation the use of specifically developed surfactants with reasonable resistance towards this
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22 harsh environment is recommended. In an ideal situation, the goal should be to have an optimum
23 salinity level for any particular surfactant. Hirasaki et al.[8] define the optimum salinity as a
24 salinity at which equal quantities of oil and water can be mutually solubilized into a
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25 microemulsion which results in equal IFTs between microemulsion phase and excess oil or
26 excess water phase[9]. Also, the water solubilisation capacity of a particular microemulsion is
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27 closely related to the partition of cosurfactants among water, oil and interfaces, chain length and
28 nature of oil [9-11]. Further research indicated that the IFT measured at the optimum salinity is
29 the minimum achievable IFT during lab experiments for IFT measurements. S.I.Chou & Shah
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30 [12] observed in their experimental research that maximum oil recovery is obtained if the salinity
31 of connate water or chemical slug is maintained at the optimal salinity of the selected surfactant.
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33 Surfactant concentration
34 Researchers all agree that concentration of the surfactant in a chemical slug always must be
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35 considerably above the critical micelle concentration so that micellization can be initiated.
36 Hirasaki et al., [8] describe the reason as: at higher concentration more of the excess oil and
37 water become solubilised and forms the middle phase or type III Winsor solution which leads to
38 higher recovery. Therefore, low surfactant concentration is not desirable. Hirasaki et al.[8]
39 reported that even if the concentration is higher than critical micelle concentrations but still close
40 to it, the middle phase was instantaneous or not detected. On the other hand, it must be kept in
41 mind that at a high concentration of surfactant end effect behavior deviates from its normal.
42 Apaydin & Kovscek [13] with their experiments showed that if the surfactant concentration is

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1 too high, it may cause the building of pressure gradient by end effect. This gradient will be from
2 the outlet toward the inlet, against the direction of flow.
3
4 Co-solvent or Co-surfactant
5 MewBot [14] demonstrated that in chemistry, a co-solvent is used in small quantities as a
6 secondary solvent to boost the power of the primary solvent and to solubilize the solute. Often

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7 co-surfactant is used in small quantities and as a second surfactant to increase the oil-solubilising
8 capacity of the microemulsion surfactant systems. One of the most common co-solvent and co-
9 surfactant is alcohol. Hirasaki et al. [8] explains that alcohol as a co-solvent softens up the

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10 surfactant film at oil/water interface and increases the equilibration rate and formation of low
11 viscosity microemulsions. However, a disadvantage of using alcohol is to decrease solubilisation
12 of oil and water in microemulsions, thus increasing the value of IFT with a certain surfactant

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13 [15]. This disadvantage might be compensated by using mixtures of cosolvents. For example,
14 Reed and Healy used mixtures of an alcohol cosolvent with synthetic alkyl/ary1 sulfonates to run
15 core flooding tests, showing the highest recovery of water flood residual oil by continuously
16 injecting surfactant [16]. This co-surfactant can change the optimal salinity required to achieve

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17 an ultra-low IFT. Despite all the advantages, this popular agent must be selected cautiously.
Hirasaki et al. (2008) explained that if surfactant selected improperly it can decrease the
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18
19 solubilisation of oil and water in the microemulsion which, therefore, increases the minimum
20 achievable IFT. In addition, if creating foam is desirable, alcohol destabilises the foam and
21 results in reduced mobility control. Until recently, the use of the co-solvent or co-surfactant in
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22 most of the cases seemed inevitable. However, many studies recently have demonstrated the
23 possibility of avoiding these additives by selecting a proper surfactant formulation and even
24 sometimes mixing dissimilar surfactants.
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25
26 Branched Surfactants
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27 Abe et al.[17] studied the microemulsion formation by mainly using branched tail
28 polyoxyethylene sulfonate surfactants. The study suggested that if in a situation using co-solvent
29 is not practical as a stabilising agent, alternatively using branched hydrocarbon surfactants at a
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30 temperature lower than 40℃ and sometimes room temperature is able to form a well stabilised
31 microemulsion. Wormuth & Zushma in [18] found the reason of using branched surfactant at
32 low temperature in phase behaviour of these surfactants in oil and water. They realised that
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33 adding salt or increasing the temperature shifts the phase diagram of the oil-rich, water-rich and
34 surfactant rich (microemulsion) system from three-phase coexistence towards the unstable
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35 emulsion zone or two-phase coexistence. However for linear surfactants the three phase
36 coexistence on the phase diagram shifts more towards the higher temperatures. Also, they also
37 concluded that the branched surfactants are more lipophilic than linear surfactants and their
38 lipophilicity is influenced by the amount and type of branching. In majority of the cases,
39 branched surfactants are less capable of mixing equivalent amounts of oil and water, which
40 clearly specifies that branched surfactant/oil/water mixtures are more distant from the tricritical
41 point than linear surfactant/oil/water mixtures.
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43 Added Chemical Group

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1 • Ethylene Oxide (EO)- C2H4O /Propylene Oxide(PO)- C3H6O

2 EPA[19] explains that Ethylene oxide with a formula of C2H4O and propylene oxide with the
3 formula of C H have been used as intermediate chemicals in the industry for different
4 applications such as a fumigant and sterility for food and hospital equipment. Wu et al.[20]
5 demonstrated that different locations of the ethylene oxide (EO) and propylene oxide (PO) in
6 molecule structure result in different scales of hydrophile–lipophile (HLB) in surfactants.

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7 Furthermore, Hirasaki et al.[8] mentioned that adding EO/PO units to the chemical structure of a
8 surfactant eliminates the need for the use of alcohol as a co-solvent to achieve low viscosity
9 micro-emulsion and ultra-low IFT. Levitt et al.[21] claim that achieving a minimum IFT value in

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10 harsh environments is possible through adding ethylene oxide unit to the chemical formulation of
11 the surfactant. The hydrogen bonding of ethylene oxide and water increases the interaction
12 energy between the brine and oil plus it helps the surfactant to be adsorbed easier at the interface

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13 of water-oil and overcome the salting out effect which results in lower IFT.
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15 • Ethoxy Unit- ( )
16 Kathel & Mohanty [22] showed that adding these anionic units increases the tolerance of

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17 surfactant in existence of divalent ions as well as the surfactant solubility in high salinity
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18 environments. They concluded that the higher the number of the ethoxy group, the higher the
19 aqueous stability
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21 • Functionalized polymeric surfactant (FPS)
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22 Functionalized polymeric surfactant (FPS) can exhibit 5% of OOIP compared to the HPAM-
23 EOR alone [23]. Surfactant-like monomers linked to the FPS backbone can pull them towards
24 the oil/water interface and create an oil/water emulsion, thus improving the microscopic
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25 displacement efficiency, although the reduction of oil/water interfacial tension is in a range of

26 0.01-0.1dyne/cm [23].
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27
28 Zeta Potential & pH
29 Zeta potential is the fundamental property in determining the stability for colloidal dispersions
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30 and emulsions. This potential is a measure of the magnitude of electrostatic repulsion/attraction

31 between suspended particles. Higher magnitude of the electrostatic repulsion/attraction results in
32 higher stability for an emulsion. Behrens [24] explains that adding acid to the emulsion causes
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33 reduction in the magnitude of zeta potential until finally it becomes neutralized or even positive.
34 The effect is opposite for adding alkali that causes the magnitude of the negative zeta potential to
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35 rise. The pH is the most important factor in affecting the zeta potential in an emulsion. Reservoir
36 pH is normally slightly acidic. As of Auttors’ knowledge today to the majority of the research in
37 literature, for long term surfactant stability at reservoir condition, it is always suggested to keep
38 the emulsion pH at slightly alkaline levels. However, the reason behind it was unclear until in
39 [25] Choi et al. evaluated the particle size distribution and surface property of a surfactant
40 emulsion by changing the pH. They realised that increasing the pH up to 12 significantly reduced
41 the mean particle diameters (p < 0.05). They interpreted the observations as: in an acidic
42 environment, protonation of surfactant occurs which, subsequently, results in inadequate
43 interfacial adsorption of the surfactant at the oil and water interface. Consequently, the

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1 aggregation of particles occurs as a result of a reduction in surfactant molecule’s surface active

2 properties. Later measuring the zeta potential of different emulsions with different pH supported
3 the accuracy of interpretations by Choi et al. (2014).
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6 Divalent Ions

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7 The existence of divalent cations mainly and , is not desirable and should be kept at
8 low levels. These cations have the potential of causing surfactant precipitation which can result
9 in blocking the pores. Anionic surfactant systems are more sensitive to the divalent ions than

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10 monovalent ions, particularly at low surfactant concentrations [26]. Due to the ion exchange in
11 the system of crude oil/brine/rock, phase behaviour becomes over optimum, leading to large
12 surfactant retention [27, 28]. Sodium metaborate has recently been introduced to sequester

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13 divalent ions as an alkali [29, 30]. If this situation is inevitable then using more resistant
14 surfactant such as surfactant with ethoxy, sulfonate or carboxylate units in their structure are
15 recommended. Details related to each surfactant are disclosed further in this article.
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17 Pressure
18 There is only limited information available on the effects of pressure on surfactant emulsion
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19 systems. Hara et al.,[31] showed that pressure can affect the critical micelle concentration
20 (CMC), however, the relationship was found not to be linear. Their measurements showed
21 indicated that increasing the pressure first increased and then decreased the CMC. This area
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22 requires more research. The studies conducted to date have not been able to discover any
23 significant impacts on the surfactant system due to pressure changes.
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25 Sulfonate/Carboxylate
26 Hirasaki [8] explains that existence of sulfonate or carboxylate unit increases the surfactants’
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27 long–term stability at higher reservoir temperatures. In addition, Shupe [32] explains that
28 sulfonate can help in the case of high salinity formation brine with a considerable amount of
29 divalent ions. However, he recommends the sulfonate application for a temperature around 50℃.
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30 Sharma and Gao [33] and Lu [34] reported that carboxylate surfactants displayed excellent
31 performance and stability at high temperature and high salinity in the existence of divalent
32 cations. These surfactants resulted in high oil recovery with low absorption in reservoir
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33 formation for both carbonate and sandstone reservoirs.

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35 Sulfate
36 Shupe [32] in his patent explained that sulfate linkage in the molecular structure of a surfactant
37 causes the molecules to be highly sensitive to temperature. This results in hydrolysis or other
38 permanent degradation of the molecules to a non-reactive form. Therefore, surfactants with
39 sulfate units are not suitable for formations with temperatures higher than surfactant critical
40 temperature on pahse envelop. This temperature is a unique characteristic of each surfactant.
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42 Surfactants and the Optimum Operating Conditions

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1 Anionic Surfactants
2 1. Alkyl Aryl Sulfonates
3 Showell [35] in his book explains that alkyl aryl sulfonates had been introduced to the market for
4 the first time in the 1930’s and shortly after in 1945 they had become the main industrial
5 surfactant component. The process for producing this surfactant involves a reaction between
6 benzene and propylene tetramer which forms alkyl aryl. Following this, the sulfonation of alkyl

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7 aryl creates alkyl aryl sulfonates. The biggest downside of these surfactants is their non-
8 biodegradability. The longer chain members of this family with C14 – C30 alkyl aryl compounds
9 are used as hydrophobes that interact well with crude oil. Hirasaki et al, [8] investigated the

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10 effects of salinity in EOR process, using C9, C12 and C15 ortho-xylene sulfonates from this
11 family of surfactants. The surfactants used in this research were made from oligomers of
12 propylene. Injecting at different salinity, they concluded that continuous injecting of each

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13 surfactant at its optimal salinity can lead to the highest recovery. The biggest advantage of alkyl
14 aryl sulfonate surfactants is their ability to be tailored based on the reservoir conditions. In
15 addition comparing to other commercially available surfactants, the raw material are accessible

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16 at low cost in the market. Shupe [32] further explains that alkyl aryl sulfonate family are
17 reasonably stable for a variety of crude oils at temperatures encountered in underground
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18 reservoirs, however, not very stable and effective in presence of high salinity or divalent ions. He
19 suggests adding co-solvent/co-surfactant if applied in high salinity environments.
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21 Figure 1- Molecular Structure of an Alkyl Aryl Sulfonate, Courtesy of OilChemTechnologies [36]
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22 2. Alkyl Benzene Sulfonate (Linear)

23 Oya et al. [37] explain that alkyl benzene sulfonate (linear) is an anionic surfactant family and
24 sub-category of alkyl aryl sulfonates with a negatively charged hydrophilic group. Furthermore,
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25 these researchers add that the length of the alkyl side chain varies between 10 and 14 carbon
26 atoms. Currently, based on the new environment protection laws, this side should be branchless
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27 since branches on alkyl side slow down the biodegradation of the surfactant in nature. The
28 existence of the sulfonate group increases the resistance of the surfactant towards temperature.
29 This surfactant is aquatic toxic and toxicity increases with increasing the water salinity or
30 hardness. Pena [38] evaluated the benefits of this surfactant family in EOR process. He observed
31 that increasing the number of carbons in the alkyl chain reduces the CMC value. In addition, this
32 surfactant family is able to reduce the IFT between water and crude oil. However, they
33 performed better with crudes with carbon number from 7 to 10.

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2 Figure 2- Molecular Structure of an Alkyl Benzene Sulfonate Courtesy of Procter&Gambl[39]

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3 3. Alkyl Sulfate (AS)
4 Alkyl sulfate is another family of anionic surfactants. According to Sigma Aldrich database [40]
5 common examples of this family are sodium lauryl sulfate, sodium dodecyl sulfate and sodium

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6 octyl sulfate, however “R’ (Figure 3) could be any hydrophobic hydrocarbon chain. Procter and
7 Gamble [41] explain that this group of surfactants biodegrade really easily. The existence of the
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8 sulfate group makes the surfactant hydrophilic and soluble in water, however since the sulfate
9 group is sensitive to temperature, the surfactant becomes insoluble in water at elevated
10 temperatures.
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11
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12 Figure 3 -Molecular Structure of an Alkyl Sulfate [42]

13 4. N-Ethoxy Sulfonate
14 According to Sharma et al. [43], n-ethoxy sulfonate is an anionic surfactant family with cloud
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15 point over 100 ℃. Sharma designed AV-70 or 7-ethoxy sulfonate and AV-150 or 15-ethoxy
16 sulfonate to study n-ethoxy sulfonate, family. This unique design took the both advantage of EO
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17 and sulfonate group at the same time. The existence of sulfonate increases the surfactant long –
18 term stability at higher reservoir temperatures. Ethoxylation of sulfonates improves their salt
19 tolerance as well. Sharma et al. indicated that unlike other anionic surfactants these surfactants
20 are stable and soluble with the injection of high salinity brine at high temperatures. Also, n-
21 ethoxy sulfonate does not precipitate in the presence of divalent ions like Ca2+ and Mg2+.

22 R = An alkyl radical, branched or linear, or an alkyl

23 n= Integer;
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1 5. Sodium Dodecyl Sulfate (SDS)

2 This anionic surfactant is one of the most popular surfactants which belongs to the alkyl sulfate
3 group. The research shows this surfactant to be a good partner for nanoparticles when injected as
4 part of an EOR process [44]. IFT is reduced by nanoparticles enhancing the surface activity of
5 anionic surfactant below its critical micelle concentration [44]. The cloud point of this surfactant
6 is over 100 ℃ [45]. However, according to Shupe [32] presence of the sulfate group makes the

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7 surfactant sensitive to the temperature and its performance decreases at high reservoir
8 temperatures. Using a mixture of nanoparticle and surfactant requires further investigation to
9 overcome the challenge of nanoparticle adsorption on the reservoir rock. Pre-coating the rocks

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10 with nanoparticles is one of suggested ways today's by researchers. However, the feasibility of
11 the idea is still unclear.

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13 Figure 4 -Molecular Structure of a Sodium Dodecyl Sulfate Courtesy of CIEC [46]
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15 6. Alcohol Propoxy Sulfate (APS)

16 Szlendak et al. [47] indicated that this surfactant is one of the main surfactants used in laboratory
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17 core floods. The structure of this anionic surfactant consists of a hydrophobe head which is C16-
18 17 branched alcohol and seven propylene oxide group. Szlendak et al. (2013) discovered that this
19 surfactant performs well when used in combination with internal olefin sulfonate (IOS) and they
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20 achieved 30% additional recovery after injecting this surfactant in tertiary recovery. The aqueous
21 and foam stability of APS is high especially in the presence of light oil at low temperatures [48].
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22 In general, this surfactant is stable at salinities up to 6000 ppm with the optimum salinity being
23 4500 ppm [49]. The only downside to this surfactant is the existence of sulfate groups which
24 makes it sensitive to temperature. [32, 41]
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27 Figure 5- Molecular structure of an Alcohol Propoxy Sulfate (APS) courtesy of [50]

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1 7. Alkyl (or Alcohol) Ethoxy Sulfate (AES)

2 This anionic surfactant is stable in high pH and salinity in the presence of alkali, and at
3 temperatures up to 83℃ for long periods of time even in the presence of divalent ions [51].
4 Procter and Gamble [41] reported that injection of diluted AES solution of 0.2 wt% in Berea
5 sandstone had resulted in additional recoveries of 35-50 % of the residual oil in place.

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7 Figure 6- Molecular structure of an Alkyl (or Alcohol) Ethoxy Sulfate (AES) Courtesy of Procter&Gamble [41]

8 8. Alpha-Olefin Sulfonate (AOS)

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9 In [52], this family of surfactants with a general chemical formula of R-CH=CH- -S Na,
10 R=C10~20 commercially recognized as sodium linear alpha olefin sulfonate was studied by
11 researchers. Their research outcome showed that this family of surfactant performs particularly

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12 well in the presence of divalent ions and has a high biodegradation rate. Rieger and Rhein [53] in
13 their book wrote that the number of carbon atoms in the structure of these surfactants varies
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14 between 10 to 20. The most common formula from this family is the one with 14 to 16 carbons
15 and it is commonly known as sodium C14-16 olefin sulfonate; C14-16-alkane hydroxy and C14-
16 16-alkene, sodium salts; sodium alpha-olefin (C14-16) sulfonate or AOS. In regards to
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17 advantages of AOS, they are stable over the wide range of pH, and exhibit good foaming and
18 detergent ability even in the existence of hard water. In numerous research work conducted to
19 date, this surfactant has been used as an alternative foaming agent. In addition, it provides a
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20 reasonable acid resistance and can be consumed in emulsion polymerisation.

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21
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22 Figure 7 -Molecular structure of an Alpha-Olefin Sulfonate(AOS) Courtesy of Wei & Navarrete [54]
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24 9. Alpha Olefin Sulfate
25 This surfactant is very similar to AOS and IOS when used in EOR processes [8]. However, as it
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26 was explained in the beginning of this article, the existence of sulfate group restricts its
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27 application in the reservoir because of its thermal sensitivity. This instability happens because of
28 the weakness of the C-O-S bond.
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30 10. Alkyl Polyalkoxy Alkyl Sulfonate or Alkyl Aryl Polyalkoxy Alkyl Sulfonate
31 In another of Shupe’s Patents [32] it is indicated that this surfactant is stable at high salinities
32 between 70,000 ppm to 220,000 ppm, even if divalent ions are present. The sulfonate group
33 increases the resistance of surfactants to high-temperature environments of up to 150 ℃ and
34 enables the surfactant to form stable foams at higher temperatures. Shupe’s Patents [32] realised
35 this surfactant performs well on its own as well as in combination with other anionic surfactants

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1 such as petroleum sulfonate, an alkyl sulfonate, or an alkyl aryl sulfonate. The number of alkoxy
2 group determines the solubility of the surfactant in a solution. Heating the emulsion can increase
3 the solubility of surfactants, however at the same time it has a negative impact on the stability of
4 the surfactant.
5
6 RO "# $ % "" '$( )

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7 R = An alkyl radical, branched or linear, or an alkyl aryl having from 8 to 24 carbon atom in the alkyl
8 chain;
9 R’= Ethyl or a mixture of ethyl and propyl with relatively more ethyl than propyl;

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10 R” = Ethyl, propyl, hydroxypropyl or butyl;
11 N= Integer from 1-20 and preferably from 2-8;
12 M+ = A monovalent cation such as ammonium, sodium, lithium or potassium. [32]

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13
14 11. Branched Alkyl Benzene Sulfonate
15 C15-18 BABS/ C16-18 BABS are the most common surfactants from this family that has been
16 used in EOR studies. This family is classified as anionic surfactants with a similar behavior to

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17 linear alkyl benzene sulfonate as explained earlier. The existence of sulfonate groups increases
18 the surfactant’s long–term stability at high reservoir temperatures. Comparing to linear alkyl
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19 benzene sulfonate, it is more expensive and it biodegrades slower. Therefore, its application is
20 declining around the world.
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22 Figure 8- Molecular Structure of a Branched Benzene Sulfonate Courtesy of Kott, Scheibel, Severson, Cripe, & Burckett-St [55]
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23 12. Docusate Sodium

24 Dang et al., [56] explain that this is a double tail anionic surfactant with a chemical formula of
25 C * H + NaO+ S .The results of the investigation conducted by these researchers on applying
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26 docusate sodium in ASP flooding indicated that it is a well-suited candidate for ASP flooding
27 especially for conventional reservoirs. Furthermore, as an outcome of this study, the phase
28 behaviour of docusate sodium in combination with the polymer (alcoflood 254S) showed that
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29 increasing the concentration of this surfactant in solution increases the viscosity of the mixture.
30 This surfactant when mixed with a commercial surfactant called Synperonic® PE/F68 made a
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31 stable mixture even at temperatures above 100 ℃ and has a considerable positive effect on EOR
32 in small and thin reservoirs. However, numerical simulation studies claim that this mixture is
33 not a good candidate for fractured or low permeability reservoirs.

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1
2 Figure 9 -Molecular structure of a Docusate Sodium Courtesy of Kott et al.[55]

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3
4 13. Ethoxy or Propoxy Glycidyl Sulfonates
5 Hirasaki et al.[8] reported that this anionic surfactant has a high solubility over an extensive

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6 range of optimal salinities. It can form a stable microemulsion with n-octane as the oil at
7 temperatures up to 120℃. However, higher temperatures and salinities may lead to phase
8 separation or reaching cloud points. Hirasaki et al. (2008) claim this sensitivity can be reduced

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9 by mixing the surfactant with more thermal stable surfactants such as internal olefin sulfonate
10 (IOS).
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11
12 Figure 10- Molecular Structure of Ethoxy Glycidyl Sulfonate Courtesy of Masaki, Furukawa, & Takenaka [57]
13 14. Alkyl Ether Sulfates
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14 Alkyl ether sulfates display a better aqueous stability compared to internal olefin sulphonates
15 [22]. The existence of sulfate in their structure makes them very sensitive to high- temperature.
16 Also, they are not very stable at high salinities [32]. Adding more ethoxy group to their structure
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17 increases the stability of the surfactants at high salinity and high-temperature environments.
18 However, using these surfactants in harsh conditions (temperature higher than 120℃ and salinity
19 greater than 180,000 ppm) is not recommended. [22]
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20
21 Figure 11- Molecular structure of an Ether Sulfate Courtesy of Andjelic et al. [42]
22
23 15. Guerbet Alkoxy Sulfate
24 Levitt et al.[21] reported that the ester linkage in sulfate structure of this anionic surfactant might
25 become hydrolyzed at temperatures above 60℃ or in low or neutral pH environments. Using
26 alkali that effectively propagated the formation assists the surfactant to become more stable at

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1 higher temperatures and this only happens over a specific range of alkalinity. Adkins et al., [51]
2 conducted the pH stability experiments for Guerbet alkoxy sulfate which indicated that at
3 elevated pH, this surfactant is reasonably stable and it is not significantly degraded even after
4 about 1.6-2.2 years at 100 ℃ or 4-6 years at 83℃ .
5
6 CnH2n+1O-POx-EOy-SO3 −

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7 Wherein
8 n= is an integer between 12 and 44, inclusive,
9 x = is an integer between 0 and 50, inclusive, and

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10 y = is an integer between 0 and 100, inclusive. [58]
11
12 16. Gemini Anionic Surfactants

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13 When it comes to the application of Gemini surfactants in EOR, work of Gao et al. (2013) is one
14 of the highlights in this area. These researchers investigated the effect of Gemini surfactants on
15 IFT as well as their stability. These compounds are named according to the length of

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16 hydrophobic tail and linking spacer group, for example in formula 14-2-14, 14 relates to the
17 length of the hydrophobic tail and 2 is the length of the spacer. There are many varieties of
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18 Gemini surfactants around. However, Gao et al. (2013) research mainly focused on 18-2-18, 20-
19 2-20, 14-4-14, 16-4-16, 18-4-18, 20-4-20, etc. Varying these numbers affects the IFT and static
20 adsorption of surfactants. CMC values in Geminis are two to three orders of magnitude lower
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21 than conventional surfactants. Gao et al. (2013) suggested in general Geminis are very stable in
22 aqueous solutions even in high temperatures (up to 85℃ ), high salinity and hard brines (up to 20
23 wt % NaCl and 5 wt% CaCl/ ) without any phase separation or precipitation. In addition
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24 achieving ultra-low IFT with these surfactants is possible and their adsorption is less than
25 conventional surfactants. Gao et al., after their vast investigation on Gemini surfactants, it was
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26 recommended that this particular surfactant could be used in harsh conditions.

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27
28 (a) (b)
29 Figure 12 (a)- Molecular Structure of a Gemini Anionic Surfactant, (b) -Molecular Structure one Anionic Gemini Surfactant
30 Courtesy of Mahanthappa, Sorenson, & Coppage [59]
31

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1
2 17. Internal Olefin Sulfonate (IOS)
3 This anionic surfactant starts from C15-C18 to C24-C28 with twin tailed hydrophobe [47]. The
4 presence of branches in this surfactant structure makes using alcohol as co-solvent under 60 ℃
5 unnecessary [8]. Levitt et al. [48] demonstrated that the presence of sulfonate unit in this
6 compound increases the surfactant long –term stability at higher reservoir temperature and makes

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7 the IOS to be stable at high temperature up to 200℃. Levitt et al. [48] in their article report this
8 surfactant as one of the main common surfactants used in core floods by researchers. It is stable
9 in aqueous solutions and forms a stable foam even at low concentration. The results of Levitt et

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10 al. (2006) investigation predicts better performance for this surfactant in low temperatures and
11 with light oils. Tertiary flooding in tight oil sandstone using this surfactant was successful and
12 could recover up to 30% of the remaining oil in place. [48] The surfactant is stable in salinity up

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13 to 6000 ppm with the optimum salinity at 4500 ppm [49]. Among all the surfactant in this group
14 C15-C18 has higher resistance towards salinity. However the stability of these groups in
15 presence of divalent ions is limited [60].

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16
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17 Figure 13 -Molecular Structure of an Internal Olefin Sulfonate Courtesy of Shi, Liao, & Liu [61]
18 18. Sulfonated, Ethoxylated Alcohol or Alkyl Phenol
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19 Shupe [32] in his patent explains that sulfonated, ethoxylated alcohol or alkyl phenol, has been
20 designed as surfactant specifically suitable for reservoirs with temperatures higher than 50℃ and
21 formation water having considerable amount of salt or divalent ions such as calcium or
22 magnesium. The sulfonate group increases the surfactant’s resistivity towards temperature and
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23 salinity without hydrolysing or becoming insoluble. The general chemical formula of this
24 surfactant family is shown in Figure 14. In addition Shupe (1978) claims that some anionic
25 surfactants such as petroleum sulfonate, alkyl sulfonate or alkyl aryl sulfonate perform well in
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26 combination with this surfactant family, however, injecting this surfactant by itself in EOR
27 processes also carries satisfactory results.
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28
29 0 (1
30 Figure 14- Molecular formula of sulfonated, ethoxylated alcohol

31 Where:
32 R= is an alkyl or alkyl aryl radical wherein the number of carbon atoms in alkyl chains varies from 8 to
33 20,
34 x =is an integer from 1 to 20
35 M+ =is a metallic cation or ammonium ion

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1
2 19. Sodium Petroleum Sulfonate
3 Loza et al.,[62] report that this family of anionic surfactants are not very stable in hard water
4 environments and tend to precipitate from solutions even in the presence of relatively low
5 concentrations (about 50-100 ppm) of divalent ions such as calcium and magnesium. Shupe [32]
6 demonstrated that the presence of sulfonate groups make sodium petroleum sulfonate reasonably

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7 stable at temperatures encountered at a majority of the reservoirs however their stability and
8 affectivity in presence of high salinity or divalent ions is not satisfying.

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9
10 Figure 15- Molecular Structure of a Sodium Petroleum Sulfonate Courtesy of Shupe (1978)

11

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12 20. TDA-9PO-Sulfate
13 Sharma and Gao et al. [33] demonstrated that Tridecyl- 9 propylene oxide- sulfate, with the
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14 commercial name of “Petrostep S13-C”, is a salt-tolerant anionic surfactant. Comparing with
15 Gemini surfactants and sodium hexadecyl sulfate, this surfactant is more hydrophobic which
16 results to more adsorption at the solid-water interface. These researchers also confirmed that
17 sulfate groups reduce the thermal stability of the molecule and only can be used up to 60 ℃.[33]
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( 2 3 ( (
18 Figure 16- Molecular Formula of TDA-9PO-Sulfate
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19 21. Alkyl Alcohol Propoxylated Sulfate

20 Wu et al. in [63] reported that this anionic surfactant is an efficient candidate for EOR. It is able
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21 to reduce IFT even at low concentrations without any assistance from co-surfactants or alkalis.
22 Some formulation from this family performs well in lowering IFT even in high salinity reservoirs
23 and could recover up to 50% of the residual oil in place in tertiary recovery only with dilute 0.2
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24 wt% surfactant concentration. Wu et al. studies indicated the disadvantage of alkyl alcohol
25 propoxylated sulfate as its high-level adsorption on sandstone comparing to other anionic
26 surfactants. In addition existence of sulfate group in this formula makes the surfactant sensitive
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27 to temperature and hence it’s not suitable for temperature above 60 ℃.

28
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(1
29 Figure 17 -Molecular Formula of an Alkyl Alcohol Propoxylated Sulfate

30 R = An alkyl radical, branched or linear, or an alkyl aryl;

31 n= Integer
32 M+ = A monovalent cation such as ammonium, sodium, lithium or potassium.

33 Nonionic Surfactants
34 1. Alkyl Ethoxy Carboxylated

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1 Friedli [64] in his book wrote that alkyl ethoxy carboxylated also known as carboxylated
2 nonionic performs as nonionic at neutral pH and anionic at alkaline pH. Furthermore, the book
3 explains that the common way of processing alkyl ethoxy carboxylated is adding sodium
4 chloroacetate to and ethoxylated alcohol. Levitt et al.[21] reported that the combination of
5 ethoxy and carboxylate group increases this surfactant’s resistivity to high temperature and high
6 salinity. The existence of ethoxy group itself in the structure of this surfactant makes the

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7 surfactant stable in high salinity environments as well as the presence of divalent ions.
8 Furthermore, Levitt et al.(2012) added that ethoxy unit forms a hydrogen bond with water which
9 increases the interaction energy of water/oil surface and, subsequently, reduces the IFT.

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10 Simultaneously, the presence of carboxylate group raises the surfactant long–term stability at
11 higher reservoir temperatures.

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12
13 RO CH2 CH2 O x CH2 COO- M+
14 Figure 18- Molecular formula for alkyl ethoxy carboxylated [65]
15 Wherein

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16 R = a C8 to C18 alkyl group
17 X= a number averaging about 1 to 15
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18 M=an alkali metal or an alkaline earth metal cation
19
20 2. Alkyl Polyglycoside (APG)
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21 Santa et al. [66] investigations on emulsion behaviour of APG in harsh conditions indicated that
22 this surfactants performs well under elevated temperatures and high salinity conditions and if co-
23 solvent is added it forms microemulsion with chain length up to 14 carbons. This stability is due
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24 to the high interaction energy between water and APG molecules. Chemical structures of the
25 glucose, leads to high solubility of APG even in the harsh environments of 180,000 ppm, and
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26 80℃ in the existence of divalent ions. This rare behaviour of APG results in low IFT under
27 various conditions.
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28
29 Figure 19 -Molecular Structure of an Alkyl Polyglycoside (APG) Courtesy of Leray [67]

30 3. NEODOL
31 Researchers from Shell [68] have designed NEODOLs surfactant for EOR purposes.
32 NEODOL alcohols are entitled based on the number of carbon atoms present in the chemical
33 formula of the product. For example, NEODOL 91 is a blend of C9, C10 and C11 alcohols. For
34 NEODOL ethoxylated or propoxylated the description of the parent alcohol is written as well as
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1 the EO or PO unit mole number, e.g. NEODOL 91 is subsequently followed by a number

2 indicating the average moles of ethylene oxide (EO) added. The recent Neodol products from the
3 Shell Company are listed in the table below. These surfactants are all nonionic and hydrophobic
4 surfactants. Researchers from Shell recently discovered that adding other surfactants such as IOS
5 to NEODOLs forms a blend which is more hydrophilic. These surfactants have been used
6 successfully up to 57℃.
7

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Alcohol Ethoxylate/ Propoxylate
NEODOL 9 NEODOL 1-5- EO NEODOL 25-12- EO
NEODOL 91 NEODOL 23-1- EO NEODOL 45-2.25- EO

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NEODOL 91-5 NEODOL 23-2- EO NEODOL 45-7- EO
NEODOL 1 NEODOL 23-3- EO NEODOL 45-13- EO
NEODOL 23 NEODOL 25-3- EO NEODOL 91-2.5- EO

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NEODOL 25 NEODOL 25-5- EO NEODOL 91-6- EO
NEODOL 45 NEODOL 25-6.5- EO NEODOL 91-8- EO
NEODOL 67 NEODOL 25-7- EO NEODOL 375 -POS
NEODOL 135 NEODOL 25-9- EO NEODOL 67-7 POS

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8 Table 1- Current Available NEODOL Products in Market Provided by Shell Company[68]

9 4. NEODOL Ethoxylate 91-8

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10 Barzegar et al., [69] explained that this nonionic surfactant is made of high-purity C9-C11
11 NEODOL alcohol with an average of 8 mole of ethylene oxide per mole of alcohol. The primary
12 alcohol of NEODOL 91-8 contains C9, C10 and C11 with a molecular weight of 160, while
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13 Ethoxylated NEODOL 91-8 has a molecular weight of 524. Barzegar et al. (2012) reported that
14 this surfactant was more effective in enhancing oil recovery for tight fractured reservoirs. As
15 mentioned above by researchers from Shell [68], these surfactants alone are not good candidates
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16 for temperature more than 60℃. However, they added that EO units increase the stability of
17 surfactants in high salinity environments with the presence of divalent ions.
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18 Figure 20- Molecular formula for NEODOL Ethoxylate 91-8

19 R =Blend of C9, C10 and C11 alcohols;

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20 n= Integer from 1-20 an average number of 8;

21
22 5. NEODOL 67 Propoxylated Sulfate (N67-7POS)
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23 Hirasaki et al.[8] reported that this hydrophobe surfactant is a NEODOL alkoxylated that contain
24 7 propylene oxide units. This product has been developed and manufactured by Shell using C16-
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25 C17 high purity primary alcohols. Flaten et al. in [70] found out a solution to improve the
26 thermal sensitivity of this compound, which is due to existence of sulfate group in using IOS in
27 combination with this surfactant at high temperatures. In [60] researchers from Shell showed that
28 the surfactant blend with IOS didn’t indicate any phase separation from cloudy solutions or
29 liquid crystalline dispersions. In addition, its performance was excellent in the presence of
30 divalent ions however it did not perform well in high salinity environments.
31
(1
32 Figure 21- Molecular Formula of NEODOL 67 Propoxylated Sulfate (N67-7POS)

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1 R = Blend of C16 and C17 alcohols;

2 N= Integer from 1-20 with an average of 7;
3 M+ = A monovalent cation such as ammonium, sodium, lithium or potassium.

4 6. Nonylphenol “N” Ethoxylate

5 According to Dow chemical company [71], this nonionic family is the sub-category of
6 alkylphenol ethoxylate. Sharma et al. (2013), who studied EOR application of NP-10 EO, NP-30

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7 EO, NP-50 EO and NP-70 EO summarising that these compounds all have cloud points over
8 100℃. They recommended that in harsh conditions of carbonate reservoir such as high
9 temperatures up to 100℃ and high salinity up to 200,000, mixture of this surfactant with a

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10 cationic surfactant increases the recovery since this mixture has higher aqueous stability
11 compared with the nonionic surfactant on its own. Furthermore, these researchers suggested that
12 the main mechanism for oil recovery by this surfactant is wettability alteration and increasing the

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13 number of EO units in Nonylphenol “N” Ethoxylate structure, adversely affects the surfactant
14 performance by reducing its wettability alteration capability and increasing the IFT of the
15 surfactant. The study showed Nonylphenol “N” Ethoxylate is able to recover up to 80% of OOIP

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16 during spontaneous imbibition. AN
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17
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18 Figure 22- Molecular Structure of a Nonyl Phenol “N” Ethoxylate, R=C9H19C6H4, 1<n<100, Courtesy of Bathe & Montgomery
19 [72]
20
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21 7. Polyethoxylated Alkyl Phenols

22 Shupe [32] wrote that this nonionic surfactant is effective for surfactant flooding in formations
23 containing high salinity water or hard water. However Shupe believed, one of the disadvantages
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24 of this family of surfactant is their low cloud point which make them insoluble at temperatures in
25 the range of 37℃ to 51℃.
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26
27 Figure 23 Molecular Structure of a Poly Ethoxylated Alkyl Phenol, Courtesy of Cristobal, Tan, Metivier, Lu, & Lambert, [73]
28
29 8. Poly (Ethylene/Propylene) Gylcol Ether

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1 Glycol ethers, depending on whether they are made from ethylene oxide or propylene oxide, are
2 labelled as either "e-series" or "p-series" glycol ethers. De and Bernhard [74] explained that this
3 nonionic surfactant family are surface active agents to increase the capillary displacement
4 efficiency of an aqueous flooding medium. Levitt et al. [21] claimed these surfactants to be
5 thermally stable because of having high cloud points and majority of them are stable in aqueous
6 solutions as well. Furthermore, this research showed the hydrophilic structure of this group

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7 makes them stable even at high salinity environments. This group is biodegradable and only a
8 few of them are considered toxic. Ethylene glycol butyl ether (EGBE), which is the most popular
9 co-solvent in EOR studies, is a member of this group and has been used in a great deal of

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10 researches to increase surfactant solubility under high salinity conditions to overcome the salting
11 out effect.

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12
13 Figure 24 -Molecular structure of Propylene Glycol Ether, n=1, 2, 3 [modified after 75]

14 9. Secondary Alcohol “N” Ethoxylate/Propoxylate

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15 According to Sharma et al. [43], these nonionic surfactants with high solubility are good
16 candidates for oil recovery. Their research showed that mixture of this surfactant and a cationic
17 surfactant had a high aqueous stability in harsh conditions such as high temperature up to 100℃
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18 and high salinity up to 200,000 ppm. Therefore, this blend is suitable for carbonate reservoirs.
Mohan [76] also reported that having cloud points over 100 ℃, these surfactants’ performance is
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19
20 stable even in high salinity formations above 35000ppm and in the presence of divalent ions.
21 Furthermore, various studies indicated that the secondary flooding with this group of surfactant
22 could recover around 80% of OOIP which is normally 60% for water flooding. The outcome of
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23 Mohan’s study claimed wettability alteration as the main mechanism of recovery while using
24 Secondary Alcohol “N” Ethoxylate/Propoxylate [76]. There is not much data available regarding
25 the temperature boundaries for this group of surfactant. However, one study on the thermal
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26 degradation of alcohol ethoxylate found that these surfactants are stable up to 300ºC in an inert
27 nitrogen atmosphere.[77]
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28
29 Figure 25- Molecular Structure of a Secondary Alcohol “N” Ethoxylate, Modified after [78]
30

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1 10. Synperonic® PE/F68

2 Dang et al. [56] used this nonionic surfactant successfully in ASP flooding with the polymer
3 (alcoflood 254S) in conventional reservoirs. The results demonstrated that this surfactant can
4 reduce the viscosity with the higher the concentration of the surfactant the higher the reduction in
5 viscosity. Consequently, Dang et al. (2012) reported that this surfactant is usually used in
6 combination with Docusate Sodium (C * H + NaO+ S) which is very effective for EOR in small

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7 and thin reservoirs. However, the simulation conducted in this study indicated that this mixture is
8 not effective for fractured or low permeability reservoirs. The optimum salinity for this mixture
9 is 3% salt concentration and the mixture is thermally stable even at the high temperature above

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10 100 ℃.
11 HO- C2H4O m- C3H6O n-H
12 Figure 26- Molecular Forlmula of Synperonic® PE/F68

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13 N= Integer from 1-20 and preferably from 2-8;
14 M+ = A monovalent cation such as ammonium, sodium, lithium or potassium.

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15
16
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Figure 27 Molecular Structure of a Synperonic® PE/F68, Modified after Berrill, Davies, Lewis, & Meakin [79]
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18 11. Tridecyl Alcohol 30 Ethoxylate(TDA 30 EO)
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19 According to Sharma et al., [43] this nonionic surfactant performs very similar to alkylphenol
20 ethoxylate family. Therefore, the results of the application of this surfactant in EOR was almost
21 identical with alkylphenol ethoxylate. These researchers reported that its application in carbonate
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22 reservoir in high temperatures up to 100℃ and high salinity up to 200,000 ppm resulted in good
23 recovery and once gain wettability alteration was detected as the main mechanism for oil
24 recovery. Injection of TDA 30 EO was able to recover up to 80% of OOIP during spontaneous
25 imbibition. According to a chemical database written by Arokor [80], increasing the number of
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26 EO units increases the hydrophilicity of the surfactant molecules and makes it more soluble in
27 water.
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28
29 C13H27 OCH2CH2 30OH
30 a

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1

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2 (b)
3 Figure 28 (a)- Chemical formula of Tridecyl Alcohol 30 Ethoxylate, (b)- Molecular Structure of a Tridecyl Alcohol “N” Ethoxylate,
4 n=30, Courtesy of AroKorHoldings [80]

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5

6 12. Triphenylmethane (TPM)

7 Siggel et al.,[81] suggested that this nonionic surfactant with a chemical formula of C/@ H/ to be

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8 classified as a viscoelastic/pseudo plastic surfactant especially at low concentration (<0.5 w/w).
9 This study showed that the surfactant has acceptable sandstone and clay injectivity and
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10 adsorption values. Although TPM is insoluble in water, it has good stability in harsh conditions
11 of high salinity (up to 18.6 % TDS), in coexistence of divalent ions and in high temperatures
12 (>70℃ . [81]
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13
14 Figure 29- Molecular Structure of a Triphenylmethane,Modified After Bhasikuttan & Mohanty [82]
15
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16 13. Tergitol Surfactants

17 Nanoemulsions have been in a central theme of surfactant EOR in recent years due to its unique
18 characteristics. The physicochemical properties of nonoemulstions shows great potential to
19 decrease residual oil saturation after water flooding. Ajay Mandal, etc., characterized the
20 physicochemical properties of nanoemulsions deployed by using Tergitol 15-S-5, Tergitol 15-S-
21 9, and Tergitol 15-S-12. Their experimental results showed that 30% of OOIP was recovered
22 after water flooding by injecting the nanoemulsions [83].
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1 Cationic Surfactants
2 1. Cetyl Trimethyl Ammonium Bromide (CTAB)
3 The other names of this compound are cetrimonium bromide, palmityl trimethyl ammonium
4 bromide, Hexadecyl trimethyl ammonium bromide. Vatanparast et al., [84] conducted an
5 investigation on phase behaviour of CTAB which showed this amine-based cationic surfactant to
6 be suitable for EOR process in carbonate reservoir and performs well in combination with nano

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7 silica particles. Studying the relationship between temperature and IFT revealed, increasing the
8 temperature leads to a reduction in IFT, however when the minimum IFT point is reached,
9 increasing the temperature further results in increasing the IFT. Observing constant high oil

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10 recovery despite high IFT value indicated that wettability alteration is the main mechanism of
11 recovery. Sharma and Mohanty (2013) managed to synthesise this compound. Their studies
12 indicated the CTAB solution in brine to be stable and clear up to 100℃ and 60,000 ppm salinity.

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13 However, the solution was not aqueous stable at temperatures above 100℃. These researchers
14 also confirmed that despite its stability, CTAB was not able to reduce the IFT to ultra-low values
15 or alter the wettability of the carbonate rock.

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16 AN
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17
18 Figure 30- Molecular structure of Cetyl Trimethyl Ammonium Bromide, Modified After Milne[85]
19
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21
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22
23 2. Coco Alkyl Trimethyl Ammonium Chloride
24 For the first time, Sharma et al. [43] patented this compound. This liquid cationic surfactant with
25 a commercial name of Arquad C-50 is made of fatty acids of coconut oil and has a cloud point of
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26 over 100℃. Mixing this surfactant with Nonyl Phenol 10 Ethoxylate increased the cloud point to
27 even higher than 130℃. The experiments conducted by Sharma et.al (2013) showed that Coco
28 Alkyl Trimethyl Ammonium Chloride was more successful in sandstone reservoir compared to
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29 carbonate reservoir in reducing the IFT and altering the wettability.

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30
31 Figure 31- Molecular structure of Alkyl Trimethyl Ammonium Chloride, Modified after Kuper & Kuzma [86]
32

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1 3. Stearyl Trimethyl Ammonium Chloride

2 Stearyl Trimethyl Ammonium Chloride with the commercial name of “Arquad T-50” is also a
3 cationic surfactant with cloud point over 100℃. This compound also was patented by Sharma et
4 al. [43] and has almost identical characteristics similar to Coco Alkyl Trimethyl Ammonium
5 Chloride. Application of this surfactant in carbonate reservoirs is not recommended since it
6 couldn’t alter the wettability of carbonate rocks efficiently.

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7

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8 Figure 32- Molecular structure of a Stearyl Trimethyl Ammonium Chloride Cortesy of Ash & Ash [87]
9
10 4. Dodecyl Trimethyl Ammonium Bromide (DTAB)
11 DTAB also was investigated by Sharma and Mohanty [43]. Similar to CTAB this cationic

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12 surfactant has a cloud point of over 100 ℃ which can be increased to 130 ℃ when mixed with a
13 nonionic surfactant. DTAB forms a clear and stable aqueous solution with injection brine of
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14 60,000 ppm TDS at temperatures under 100℃. The study conducted by Sharma and Mohanty
15 (2013) suggested DTAB is able to alter the wettability from oil-wet to intermediate water-wet in
16 carbonate rock samples. However, it could not reduce the IFT to ultra-low values. The mixture
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17 of these nonionic and DTAB in dilute concentrations can recover up to 80% of the OOIP even in
18 harsh conditions of carbonate reservoir. This value is 70 % for injecting only DTAB on its own
19 in low concentration.
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20
21 Figure 33- Molecular Structure of a Dodecyl Trimethyl Ammonium, Courtesy of ChemNet [88]
22
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23 5. Ethoxylated Alkyl Amine

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24 According to Chen et al. [89], ethoxylated alkyl amine performs as a cationic surfactant when
25 carrying low numbers of the EO group in its molecular structure. Adding a higher number of EO
26 units to the surfactant makes it perform more like a nonionic surfactant. The existence of the EO
27 and R units in this compound increases its cloud point to higher temperatures. The higher
28 resistance of surfactants by increasing the number of the EO group happens as a result of making
29 the surfactant more hydrophilic. However, for achieving the unusual temperatures over 120℃,
30 requires an additional hydrophilic group. One of the most common protonated groups is an
31 amine. Chen et al. (2012) investigation on carbonate reservoir indicated that this surfactant can

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1 even be a good candidate for forming a stable CO2/water foam at high temperatures and salinities
2 (up to 180,000 ppm).

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3
4 Figure 34- Molecular Structure of an Ethoxylated Alkyl Amine, Modified After Welton, Todd, & McMechan [90]
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6

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7 Surfactant Mixtures
8
9 1. Combination “A”- Mixture of Alkyl Ether Sulfate and Alkyl Propoxy Ethoxy Sulfate

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10 Mohan [76] reported that the mixture of these two surfactants is successful in lowering the IFT
11 (as low as 10 dynes/cm) and altering the wettability from oil-wet to intermediate or slightly
12 water-wet in harsh conditions of low permeability (2-5 md) reservoir. Mohan (2009) explained

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13 that it has performed well in high salinity solutions of up to 45000 ppm TDS in the presence of
14 divalent ions. 36000 ppm TDS is estimated as an optimum operating condition. The presence of
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15 sulfate groups increases the sensitivity of the surfactant to high temperatures. Mohan (2009)
16 indicated that this mixture is successful at temperatures up to 52 ℃ and is able to result in the
17 additional recovery of 28 % of the residual oil in place. Furthermore, Mohan tested another
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18 mixture which he referred to as combination “B”. Further details about this mixture are presented
19 below.
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21
22 2. Combination “B”- Mixture of Alkyl Propoxy Sulfate and Alkyl Ethoxy Sulfonates
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23 The second mixture, “B”, which is slightly different from mixture “A” has also been tested by
24 Mohan [76] on samples representing a low permeability (2-5 md) carbonate reservoir. The
25 results have shown that combination “B” emulsion is effective even in high salinities of up to
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26 45000 ppm TDS and in the presence of high divalent ions. The surfactant performance in
27 lowering the IFT (down to 10 dynes/cm) and changing the wettability of carbonate rocks from
28 oil-wet to intermediate or to slightly water-wet, is quite similar to mixture “A”. Similar to
29 mixture “A” the optimum salinity for this surfactant is also 36000 ppm TDS, however the
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30 tertiary recovery using this blend has resulted in extra 14 % oil recovery which is almost half of
31 the recovery using mixture “A”. The study suggested further investigation on the types of rocks
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32 as the lower recovery with mixture B could be related to the mineralogy of the specific type of
33 rock samples used for the test and results could be different for other types of rocks.
34
35 Bio Surfactant
36 Bio-based surfactants have fascinated scientists due to their renewable resources and outstanding
37 surface properties [91]. Sen [92] stated that microbial enhanced oil recovery was initiated in
38 1947. Sen [92] explained that the Biotechnological recovery process consists of injecting
39 carefully chosen groups of natural bacteria into the reservoir to improve oil recovery through

24
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1 specific metabolic events. Sen in his article specifies that bacteria such as Bacillus sp,
2 RLichenysinhamnolipid Acinetobacter, Emulsan, Alasan, Pseudomonas, Rhamnolipid,
3 Rhodococcus,Viscosin and Trehaloselipids are among the most applied bio surfactants in the
4 EOR process. Sen classified the reasons for slow employment of bio surfactants in EOR process
5 as unpredictability in situ performance, low ultimate oil recovery factor, uncertainty about
6 meeting the engineering design standards by microbial processes and a general hesitation about

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7 processes involving live bacteria.
8 Torres et al., [93] investigated the difference in performance of natural surfactants (one produced
9 by a bacteria and two of vegetal origin) to synthetics surfactants (cationic, anionic, non-ionic and

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10 zwitterionic) for its potential use in enhanced oil recovery EOR application. Torres eat al, [93]
11 concluded natural surfactant rhamnolipid which is created by Pseudomonas and guar gum
12 exhibited similar and sometimes better, surface tensions, foaming capabilities, resistance to high

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13 salinity up to 46,800 mg/L, and resistance to high temperatures up to 70 °C compared to the
14 synthetic surfactants normally used in EOR processes. An investigation by Daoshan et al. [94] on
15 using biosurfactant-rhamnolipid-fermentation liquor (RH) as a sacrificial agent showed that loss

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16 of ORS due to static adsorption can be reduced by 25–30% when RH is mixed with ORS or pre-
17 adsorbed on sandstone. The core-flooding experiments showed that enhanced oil recovery with
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18 the formulation of ASP of 0.2 wt.% RH and 0.15 wt.% ORS is 7% more than that with the
19 formulation of ASP of only 0.15 wt.% ORS, and is equal to that with the formulation of ASP of
20 0.3 wt.% ORS. Result of Daoshan et al [94] research revealed that using RH is able to reduce the
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21 cost of ASP flooding. Injecting formulation of ASP of 0.2 wt.% RH and 0.15 wt.% ORS in a
22 pilot scale resulted in 16.6%(OOIP) enhanced oil recovery in the entire area of the experiment.

Zwitterionic Surfactant
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23
24 This particular type of surfactant usually refers to the amphiphilic organic compounds that holds
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25 both hydrophobic groups in their tail and hydrophilic groups in their heads. Only recently this
26 type of surfactant gained attention in the oil and gas industry. To the knowledge of writers there
27 has not been significant research on the application of zwitterionic surfactants in EOR. One of
28 the highlighted studies in this area took place by Zhang et al., [91].These researchers created a
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29 novel zwitterionic surfactant derived from castor oil. When dispersed in water the surfactant
30 could reduce the interfacial tension between crude oil and water to ultra-low value as 5.4 × 10−3
31 mN/m at low concentration of 0.010 g/L in the absence of any alkali. Zhang et al., [91] showed
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32 that this bio-based surfactant has strong electrolyte tolerance, temperature resistance and thermo
33 stability, better wetting and foaming performance which makes it a potential oil recovery
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34 enhancer.
35
36 Conclusion:
37 A comprehensive review of the existing surfactants and surfactant mixtures and their application
38 for EOR processes has been presented. Below are the main conclusion which can be drawn from
39 this review:
40 • Surfactants are classified as anionic, cationic, nonionic, bio surfactant and zwitterionic
41 surfactants.
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1 • Majority of cationic surfactants form stable solutions in brine.

2 • Nonionic surfactants are effective for surfactant flooding in formations containing high
3 salinity water or hard water.
4 • For carbonate reservoirs, cationic surfactants or mixtures of them with nonionic
5 surfactants are the most effective EOR agent. They increase the production mainly
6 through wettability alteration.

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7 • In contrast, anionic surfactants are not good EOR agents for carbonate reservoirs and
8 their combination with the cationic type surfactant reduces the production.
9 • Anionic surfactants are the most effective candidate for sandstone reservoir either on

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10 their own or in the mixture with other anionic surfactants.
11 • A problem with stability and effectiveness of surfactant solutions rises when they are
12 used in specific temperature conditions in the range of 70° C to 120 C and above, high

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13 pressures (e.g. 4,000 psi), and high concentrations of divalent metals such as calcium,
14 magnesium, etc. (e.g. up to 3,000 ppm or more) and high salt content (e.g. 180,000 ppm
15 or more).
•

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16 Solving the problem of emulsion stability and viscosity in reservoir is possible through
17 choosing suitable chemical units and their numbers plus tuning the pH level. Stability is
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18 assessed by measuring zeta potential. The higher this magnitude shows higher stability
19 for the emulsion. For EOR process slightly alkali pH is recommended.
20 • The type and number of the chemical units in a surfactant formula affects the ability of
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21 the surfactant in reducing the IFT, altering the wettability, decreasing/increasing the
22 viscosity, thermal stability and its resistance in high salinity and hardness conditions.
23 • Using ethylene oxide propylene oxide units or branched surfactants eliminate the need to
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24 use co-solvent to reach low IFT and viscosity.

25 • Using of Ethoxy unit increases the tolerance of the surfactant in the existence of divalent
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26 ions as well as the surfactant solubility in high salinity environments.

27 • Sulfonate group increases the thermal stability of surfactant and sulfate on the other hand
28 decreases its thermal stability.
•
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29 Carboxylate surfactants displayed good performance and stability at high temperatures,

30 high salinity with existence of divalent cations.
31
Type of Cationic Anionic Nonionic Zeitterionic
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surfactant
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Advantages -Form stable -Effective -Effective for New generation

solutions in brine candidate for surfactant of surfactants,
sandstone flooding in has strong
-Cationic reservoir formations electrolyte
surfactants or containing high tolerance,
mixtures of them salinity water or temperature
with nonionic hard water. resistance and
surfactants are the thermo stability,
most effective better wetting
EOR agent for and foaming
carbonate performance

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reservoirs
Dominant Reducing IFT and Reducing IFT Reducing IFT Reducing IFT
Mechanism Wettability and Wettability
Alteration Alteration
1
2
3

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4
5
6

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7
8
9

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10
11
12

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